Molecular interaction and properties of poly(ether ether ketone)/liquid crystalline polymer blends incorporated with functionalized carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were functionalized with a carboxyl group (-COOH) to achieve better interfacial adhesions with both phases of the poly(ether ether ketone) (PEEK) and liquid crystalline polymer (LCP) in their blend. These strong interfacial interactions among the functionalized MWCNTs, PEEK and LCP improved the mechanical properties of the polymer blend. Three different weight percentages (0.6%, 1.2% and 1.8%) of acid modified CNTs were used with PEEK-LCP blend, for the preparation of nanocomposites. In PEEK-LCP blend, the ratio of PEEK and LCP was maintained as 10:6 respectively. The tensile strength and modulus of the composites were improved by 51% and 73% respectively with the incorporation of only 1.2% of MWCNT-COOH as compared to the unfilled PEEK/LCP blend. Moreover, careful studies of the molecular interaction, morphological, dynamic mechanical and thermal properties confirmed that a better miscibility between PEEK and LCP had been constituted in the presence of MWCNT-COOH. Therefore, it was found that the functionalized MWCNTs not only played the traditional role as reinforcing filler, but also performed a novel role as a compatibilizer for the PEEK/LCP blends.     

可全生物降解PLA/PBAT/PHBV共混材料的结构与性能

为了得到刚性与韧性平衡的聚乳酸（PLA）基可生物降解共混材料,通过熔融共混挤出法制备了不同质量比的PLA/己二酸-对苯二甲酸-丁二酯共聚物（PBAT）/聚（3-羟基丁酸-co-羟基戊酸共聚酯（PHBV）可全生物降解共混材料,采用SEM、TG、DSC、毛细管流变仪和万能材料试验机对PLA/PBAT/PHBV共混材料的形态结构、热性能、流变性能和力学性能进行了研究。结果表明:PLA/PBAT/PHBV共混材料的热失重起始分解温度相对纯PHBV提高了45 ℃,热稳定性提高;共混体系中各组分的玻璃化转变温度与单一体系相比几乎无变化,PLA/PBAT/PHBV共混体系为完全不相容体系,同时PBAT和PHBV的加入阻碍了PLA的冷结晶;PLA/PBAT/PHBV 共混体系的共混形态呈“海-岛”分布,PBAT和PHBV均匀地分散于PLA基体中,相界面分明;随着PBAT含量增加,PLA/PBAT/PHBV共混材料熔体的流动性增加,温度变化对黏度的影响变大;PLA/PBAT/PHBV质量比为70/20/10的共混材料可在保留纯PLA 60%拉伸应力的同时,拉伸应变提高到纯PLA的2.6倍,韧性得到改善。所得结论表明PLA/PBAT/PHBV质量比为70/20/10的共混材料的综合力学性能较纯PLA好。      

Phase behaviour and mechanical properties of poly(ether ether ketone)-poly(ether sulphone) blends

The phase behaviour and the mechanical properties of binary blends composed of poly(ether ether ketone) and poly(ether sulphone) have been studied both in the amorphous state and after crystallization of poly(ether ether ketone).Differential scanning calorimetry and dynamical mechanical analysis clearly show the existence of phase separation in the blends. Density measurements confirm the absence of strong interactions between the blend components, as well as the slight effect of PES on the crystallization of PEEK.The mechanical properties of the quenched, amorphous blends remain surprisingly good in spite of the observed immiscibility, however, slowly cooled, crystalline blends appear as brittle materials.     

聚醚醚酮及其共混物的研究EI

综述了高性能树脂聚醚醚酮及其共混物的研究现状，讨论了聚醚醚酮的形态结构、结晶和熔融双峰行为及力学性能的研究，指出了共混物的分子结构对相容性、形态结构及力学性能的影响，说明共混使所得高分子材料的性能更多样化。     

生物降解聚酯PLA/PBSA共混体系的制备与结构性能

采用熔融共混法制备了PLA/PBSA共混材料;采用DSC,TG,DMA和拉伸力学试验研究了该共混体系的热性能和力学行为;采用土壤悬浊拟环境降解实验法研究了共混材料的生物降解性;同时对该体系的生物降解机理及影响因素进行了初步探讨。结果表明,PLA/PBSA为非均相结晶/结晶高分子共混体系;PLA含量增加,有利于提高材料的模量和拉伸强度;增加PBSA的含量,可以提高PLA/PBSA共混体系的环境生物降解性。PLA/PBSA是力学性能和降解性能互补的生物降解材料。     

碳纤维增强聚醚醚酮复合材料的形状记忆效应

为推动形状记忆聚合物在空间等极端恶劣环境中的应用,以超薄碳纤维增强聚醚醚酮(Carbon fibers reinforced polyether-ether-ketone,CF/PEEK)预浸料为实验对象,采用薄膜叠层与热压成型工艺制备厚度为0.036 mm超薄预浸料的层合片材,研究了其在热应力驱动下的形状记忆行为。结果表明,在320℃加热-冷却热循环温度场的作用下,CF/PEEK复合材料超薄层合板的初始变形的形状回复率近似可达100%,当变形循环达到100次时,其形状回复率仍然可以保持在90%以上。此外,根据层合板变形的温度与应力-应变关系,解释了CF/PEEK复合材料的热应力驱动变形机制。在此基础上,改变CF/PEEK层合板厚度进行仿真设计,实现了初始状态与深海珊瑚形状、立方体、灯笼草形状之间的变形与回复。利用记忆变形产生的机械夹紧力,完成了硬币抓取实验,验证了CF/PEEK复合材料在主动变形结构应用的可行性。      

PPENK增韧改性BMI树脂体系的制备与性能

采用溶液法制备了杂萘联苯聚芳醚腈酮(PPENK)/双马来酰亚胺树脂(BMI)共混体系。通过差示扫描量热法(DSC)对共混体系固化反应动力学进行了研究,固化活化能为85.8 kJ/m2。采用冲击和拉伸实验考察了PPENK含量对共混体系力学性能的影响,共混体系的冲击强度为1.83 kJ/m2～2.95 kJ/m2,拉伸强度为68 MPa～84 MPa,拉伸模量为1.14 GPa～1.53 GPa。通过对固化物断面的扫描电镜(SEM)分析了增韧机理,改性后的BMI树脂在断裂时发生了塑性变形。通过热重分析法(TGA)研究了体系的耐热性,共混体系在氮气气氛中5%热失重温度为420℃～426℃。     

聚乳酸/酯化纤维素纳米晶体共混膜性能研究

以聚乳酸(PLA)为基体,酯化纤维素纳米晶体(ECNC)为添加剂,制备了PLA/ ECNC共混膜。探讨了原始纤维素纳米晶体(CNC)与ECNC对PLA膜的透光率、表面形貌、热稳定性、亲疏水性及力学性能的影响。结果表明,与CNC相比,ECNC与PLA的相容性提高,透光率、热稳定性及力学性能也显著增强;经酯化的纤维素纳米晶体能降低CNC的亲水性,从而增强与PLA的界面黏合力,使CNC在PLA共混膜中的质量分数由小于1%提高到5%。该PLA/ECNC共混膜在包装塑料领域具有潜力,为制备出性能更加优良的可降解包装用塑料提供了一种简单可行的方法。     

Thin film and bulk deformation behaviour of poly(ether ether ketone)/poly(ether imide) blends

The deformation behaviour of amorphous thin films of poly(ether ether ketone) (PEEK)/poly(ether imide) (PEI) blends was investigated over a wide temperature range by optical and transmission electron microscopy. All the materials showed localized shear deformation at temperatures well below Tg. In pure PEI and in blends with up to 60 wt% PEEK content, a transition from shear deformation to disentanglement crazing occurred as the temperature was raised. However, this transition was absent in PEEK, which deformed by shear over the whole temperature range, and similar behaviour was found for PEI/80 wt% PEEK. It is argued that at high PEEK content disentanglement crazing is suppressed by strain-induced crystallization and some evidence for crystalline order in deformed regions of initially amorphous PEEK thin films was obtained by electron diffraction. The thin film deformation behaviour of the blends was also shown to be consistent with their bulk deformation behaviour, a high temperature ductile–brittle transition being observed at low PEEK content in tensile tests. This revised version was published online in November 2006 with corrections to the Cover Date.     

碳纤维-AlN/聚醚醚酮复合材料的制备与性能

以聚醚醚酮(PEEK)为基体树脂、碳纤维(CF)和氮化铝(AlN)为填料,通过模压成型的方法制备了抗静电耐热型CF-AlN/PEEK复合材料。采用高阻计、导热系数测定仪、热失重、差示扫描量热仪和SEM研究了CF-AlN/PEEK复合材料的抗静电性能、热性能、力学性能以及降温速率对复合材料性能的影响,并探讨了后期热处理对力学性能的影响。结果表明:当CF和AlN的质量分数均为10%时,CF-AlN/PEEK复合材料的性能较优,其表面电阻率达到108 Ω,比PEEK的表面电阻率提高了6个数量级;导热系数为0.418 W·(m·K)-1,初始分解温度高达573℃;拉伸强度提高了40.4%;降温速率越低,复合材料的熔点越高;后期热处理会影响CF-AlN/PEEK复合材料的力学性能,在270℃下热处理2 h,其拉伸强度可达146 MPa,表明在生产过程中,加工温度是影响复合材料性能的因素之一。      

聚醚醚酮和烯丙基化合物改性双马来酰亚胺复合材料微观结构及力学性能

采用浓H₂SO₄氧化聚醚醚酮（PEEK）得到磺化聚醚醚酮（SPEEK）,以3,3'-二烯丙基双酚A （BBA）、双酚A双烯丙基醚（BBE）为活性稀释剂、SPEEK为改性剂、双马来酰亚胺（BMI）树脂为基体,浇注成型制备SPEEK/BBA-BBE-BMI复合材料,同时研究了SPEEK的改性效果及复合材料微观形貌与力学性能。结果表明：SPEEK改性效果较好,在FTIR中存在明显的磺酸基团特征峰,SEM和能谱分析表明,SPEEK微观形貌变化明显,硫元素含量较高;SPEEK/BBA-BBE-BMI复合材料的微观形貌显示,SPEEK在基体中呈现直径为2 μm左右的多孔状两相结构,且分散均匀,此多孔结构改善了复合材料的断裂形貌,由脆性断裂转变为韧性断裂,当断裂纹遇到SPEEK组分时受阻而出现不规则发散,此变化会赋予复合材料更加优异的性能。力学性能测试结果显示,当SPEEK含量为5wt%时,SPEEK/BBA-BBE-BMI复合材料的弯曲强度和冲击强度达到最佳,分别为147.93 MPa和15.74 kJ/mm²,分别比基体提高了49.47%和66.21%。     

Novel degradable compound shape-memory-polymer blend: Mechanical and shape-memory properties

Considering the mechanical properties and shape-memory properties, we developed a novel biodegradable compound shape-memory-polymer blend composed of poly (l-lactide-co-ε-caprolactone) (PLLCA) and poly (l-lactide-co-glycolide) (PLLGA). In comparison with most reported shape-memory blends, our blend showed outstanding shape-memory properties at higher stationary-phase concentrations (more than 50% w/w). The results of scanning electron microscopy (SEM) demonstrated the immiscibility between PLLCA and PLLGA. The tensile test results revealed that blends with different PLLGA concentrations showed different mechanical properties. The results of the shape-memory tests suggested that the blends showed improved recovery and fixing performances with an increase in the PLLGA content, especially at PLLGA concentrations greater than 50 wt.%.     

Effect of carbon nanotubes on the mechanical properties and crystallization behavior of poly(ether ether ketone)

Pristine carbon nanotubes (CNTs) and noncovalently functionalized carbon nanotubes (f-CNTs) were used to prepare poly(ether ether ketone) (PEEK) composites (CNTs/PEEK and f-CNTs/PEEK) via melt blending. Noncovalently functionalized multiwalled nanotubes were synthesized using hydrogen-bonding interactions between sulfonic groups of sulfonated poly(ether ether ketone) (SPEEK) and carboxylic groups of nanotubes treated by acid (CNTs–COOH). The effects of these two kinds of nanotubes on the mechanical properties and crystallization behavior of PEEK were investigated. CNTs improved mechanical properties and promoted the crystallization rate of PEEK as a result of heterogeneous nucleation. Better enhancement of mechanical properties appeared in the f-CNTs/PEEK composites, which is ascribed to the good interaction between f-CNTs and PEEK. However, the strong interaction of f-CNTs and PEEK chains decreased the crystallization rate of PEEK for high content of f-CNTs.     

Properties of epoxidized palm oil plasticized polytlactic acid

In this study, epoxidized palm oil (EPO) was utilized as a plasticizer for polylactic acid (PLA) using chloroform as a solvent by solution casting process at six weight ratios of PLA/EPO, 95/05, 90/10, 80/20, 70/30, 60/40, and 50/50, respectively. Fourier-transform infrared (FTIR) spectroscopy was used to identify the functional groups of PLA, EPO, and PLA/EPO blends. Thermal stability, mechanical, and morphological properties of the blends were investigated by thermogravimetric analyzer (TGA), tensile properties measurements, and scanning electron microscope (SEM) technique, respectively. The FTIR spectra indicate that there are some molecular interactions by intramolecular hydrogen bond between PLA and EPO. All sets of PLA/EPO blends show high thermal stability and significant improvement of mechanical properties compare to pure PLA. The highest elongation at break (about 210%) was obtained when the ratio of PLA/EPO blend was 80/20. Morphological results of PLA/EPO blends show that ESO was good miscible with PLA.     

聚芳醚腈/双邻苯二甲腈树脂共混改性与性能研究

通过联苯型双邻苯二甲腈与聚芳醚腈熔融共混形成预聚物,经高温固化及后热处理制备了聚芳醚腈/双邻苯二甲腈共混体系,研究了其耐热性能、力学性能、形貌特征以及其微观结构与性能之间的关系。其共混体系固化物的弯曲强度,断裂弯曲应变等性能较纯双邻苯二甲腈树脂均有大幅度的提高,并且保持了纯双邻苯二甲腈树脂耐高温,高模量等优越性能。当聚芳醚腈的含量达到12%时,该体系的弯曲强度和断裂弯曲应变较纯双邻苯二甲腈固化物分别高了52.7%和61.6%,实现了热固性基体树脂的同时增韧增强而不降低耐热性的改性技术路线。     

Morphology,interfacial and mechanical properties of polylactide/poly(ethylene terephthalate glycol) blends compatibilized by polylactide-g-maleic anhydride

Polylactide/poly(ethylene terephthalate glycol) (PLA/PETG 80/20 wt) blends compatibilized with polylactide-g-maleic anhydride (PLA-g-MAH) were prepared by melt blending and the rheological, morphological and mechanical properties of the blends were studied. PLA/PETG (80/20 wt) blend formed a typical sea-island morphology, while upon compatibilization, the size and size distribution of the dispersed phase decreased significantly and the 3 wt% PLA-g-MAH compatibilized blend exhibited the smallest phase size and the narrowest distribution of the dispersed particles. The interfacial tension between PLA and PETG was determined from the morphological characteristics and the viscoelastic response of PLA/PETG blends via using two emulsion models. A minimum for PLA/PETG blend containing 3 wt% PLA-g-MAH was observed from both Palierne model and G–M model. The elongation-at-break increased by ∼320%, from 6.9% for PLA to 28.7% for the blend containing 3 wt% PLA-g-MAH without significant loss in the tensile modulus and tensile strength.     

Toughening of brittle poly(lactide) with hyperbranched poly(ester-amide) and isocyanate-terminated prepolymer of polybutadiene

Abstract  

The use of polylactide (PLA) in durable applications is currently being hampered by its brittleness and low impact strength. In this study, the effects on mechanical properties of two potential toughening agents for PLA, i.e., hydroxyl-terminated hyperbranched poly (ester amide) and isocyanate-terminated prepolymer of butadiene (ITPB), alone and in combination, are investigated with the aim of making tough PLA blends for use in durable non-food applications such as automotive interior. Synergistic effects in impact strength were observed in PLA ternary blends containing hyperbranched polymer (HBP) and ITPB. Impact strength of the PLA/HBP/ITPB ternary blend was improved by over 86 %, while the elongation at break was increased by over 100 %. Physical and chemical interactions between the hydroxyl-terminated HBP and the ITPB may be responsible for the observed synergistic effect and improvements in impact strength. Tensile, flexural, thermal, and thermo-mechanical properties of the PLA/HBP blends with varying amounts of the ITPB were studied. Scanning electron microscopy images showed evidence of stretched polymer which may indicate that the fracture behavior of PLA changed from brittle to ductile in the PLA/HBP/ITPB ternary blends.     

热塑性聚氨酯/聚己内酯共混物的形状记忆和力学性能

利用简单的熔融共混制备得到不同组分比的热塑性聚氨酯(TPU)/聚己内酯(PCL)共混体系,研究了两相组分比的变化对共混材料相形态、形状记忆性能和力学性能的影响。偏光显微镜观察发现,随着结晶相PCL含量的增加,其逐渐从分散相过渡至连续相再发展为基体相。热性能测试结果表明TPU的加入对PCL的熔融行为影响甚微,整个共混体系基本表现出与PCL一致的熔点。形状记忆性能测试发现共混材料的形状记忆性能表现出明显的组分依赖性,并在组分比为50%/50%性能达到最优(R_r=91%,R_f=96%)。而力学测试结果表明,PCL的加入既不会显著劣化TPU原有的拉伸强度,还能进一步提高其断裂伸长率。     

A review of shape memory polymer composites and blends

Shape memory polymers (SMPs) are a kind of very important smart polymers. In order to improve the properties or obtain new functions of SMPs, SMP composites and blends are prepared. We thoroughly examine the research in SMP composites and blends achieved by numerous research groups around the world. The preparation of SMPs composites and blends is mainly for five aims: (1) to improve shape recovery stress and mechanical properties; (2) to decrease shape recovery induction time by increasing thermal conductivity; (3) to create new polymer/polymer blends with shape-memory effect (SME); (4) to tune switch temperature, mechanical properties, and biomedical properties of SMPs; (5) to fabricate shape memory materials sensitive to electricity, magnetic, light and moisture. The trend of SMP composite development is discussed. SMP composites and blends exhibit novel properties that are different from the conventional SMPs and thus can be utilized in various applications.     

聚醚醚酮改性研究进展

聚醚醚酮(PEEK)作为一种新型高性能热塑性工程塑料,在许多工程领域有着广泛的应用.采用不同手段增强PEEK,改善其加工性能和力学性能、热性能、摩擦学性能,有利于降低材料成本和进一步拓展应用范围.本文从纤维增强PEEK、颗粒填充PEEK、PEEK表面改性、与聚合物共混等方面综述了PEEK改性研究的进展情况.